Coloration of material



Patented Sept. 19, 1933 COLORATION 0F MATERIAL George Holland Ellis, Henry Charles Olpin, and William Bertram Miller, Spondon, near Derby, England, assignors to Celanese Corporation of America, a corporation of Delaware No Drawing. Application September 27, 1932, Serial No. 635,042, and in Great Britain October 9 Claims.

This invention is a continuation in part of the invention of prior U. S. application S. No. 424,442 filed 29th January, 1930 and relates to the coloration of textile materials made of or containing organic derivatives of cellulose.

U. S. application S. No. 424,442 describes the production of black shades on materials made of or containing cellulose acetate or other cellulose esters or ethers by the oxidation thereon of aniline in the presence of mineral acid in quantity chemically equivalent thereto, there being present in addition a quantity of a substance having an acid reaction, for example a mineral or organic acid, or an acid salt, or a salt havingan acid reaction, but preferably an organic acid. By padding a cellulose acetate fabric with a liquor made up with aniline hydrochloride, acetic acid, and the necessary additions, and subsequently ageing, full ungreenable black shades of a quality leaving little to be desired may be obtained with great ease.

We have now found that as the additional acid reacting substance formic acid has pro-eminent advantages over organic acids in general, especially when it is desired to apply the coloration by printing or other methods of application involving the use of thickened preparations.

According to the present invention therefore formic acid is employed as the organic acid in the production of black colorations by the process of U. S. application S. No. 424,442.

The present invention is of particular value in that it enables the easy production of full aniline black prints on materials made of or containing cellulose acetate or other esters or ethers of cellulose.

In carrying the invention into effect the aniline and equivalent quantity of mineral acid may conveniently be applied to the materials in the form of mineral acid salts of aniline. There may, for example, be applied to the materials by printing or other means of local application thickened compositions containing the aniline salt, e. g. the hydrochloride or nitrate, and also containing formic acid and an oxidizing agent, for example a chlorate with or without oxidation catalysts such as salts of vanadium, copper, or iron. After printing and drying, the materials may be aged, chromed and soaped according to the usual methods when full ungreenable black pattern effects are obtained. Again the materials may be padded with a solution or liquor containing the aniline salt, formic acid and an oxidizing agent, with or without other substances such as catalysts. After padding and drying the materials are aged, chromed and soaped when excellent full blacks are obtained. The invention is not, however, limited to the application of the aniline salt, formic acid and oxidizing agent by padding or printng, nor to the application of these substances in a single operation. For example, the aniline salt, formic acid and oxidizing agent may be applied by a,simple passage of the material through a bath containing them, or they may be applied in succession by padding the material with, or passing the material through, two or more solutions each containing one or more of the necessary compounds. Furthermore, other substances having an acid reaction whether inorganic or organic may be employed in addition to formic acid and mineral acid equivalent to the aniline. Thus, for example, acetic, gylcollic, or lactic acids or any of the acidic bodies used in the production of aniline blacks in U. S. application S. No. 424,442 may be employed together with formic acid in the process of the present application.

When dyeing cellulose ester or ether materials in black shades according to the present invention, white or colored pattern effects may be' simultaneously produced thereon. Thus for example pattern eifects may be produced on the material according to any of the processes mentioned in U. S. application S. No. 424,442.

The following examples illustrate the present invention without in any way limiting it:-

Example 1 A solution containing:

Parts Aniline salt 15 Formic acid 3 Methylated spirits 12 Gum arabic 1:1 70 is mixed with a solution containing: Sodium chlorate 9. 6 Cupric chloride 0. 4 Water 10. 0

and immediately printed on to a cellulose acetate fabric by means of a roller having a suitable design. The material is then dried, aged for 3 to 4 minutes in dry steam in a Mather and Platt ager, and then further treated in a bath containing 5 grams per litre of sodium bi-chromate and 5 cos. per litre of glacial acetic acid at 50 for 5 minutes. After this treatment the material is rinsed, soaped for 10 minutes at C. and

finally rinsed and dried when full ungreenable black pattern effects are obtained.

Example 2 A solution containing:

Parts Aniline salt 20 Methylated spirits 16 Formic acid 4.4 Oleyl diethyl-ethylene diamine 0.08 Gum arabic 2: 1 58 is mixed with a solution containing: Sodium chlorate 12. 8 Cupric chloride 0. 64 Water 7. '76

and immediately applied to a woven fabric consisting of cellulose acetate. The material is then treated according to the method described in Example 1 when a full ungreenable black is obtained.

Example 3 A cellulose acetate fabric is padded with a solution containing:

Parts Aniline salt 12.50 Sodium chlorate"; 9. 60 Methylated spirit 10.00 Cupric chloride 0.40 Oleyl diethyl-ethylene diamine 0. 05 Formic acid 2.75 Water 64. 50

the conditions being so regulated that the fabric retains its own weight of padding liquor. It is then aged for 5-7 minutes in dry steam in a Mather & Platt ager and further treated according to the method described in Example 1 when a full ungreenable black is obtained.

While the invention has been described more particularly in connection with the coloration of materials made of cellulose acetate,.it is also applicable to the coloration of materials made of or containing other cellulose esters, for example, cellulose formate, cellulose propionate, or cellulose butyrate, or the products-obtained by the treatment of alkalized cellulose with esterfying agents, e. g. the product known as immunized cotton obtained with para toluene sulpho chloride, or of cellulose ethers for instance methyl, ethyl or benzyl cellulose, or the products obtained by the reaction of cellulose and glycols or other polyhydric alcohols, ortmade of or containing mixtures of two or more of these products. The invention may also be applied to the dyeing or otherwise coloring of materials containing one or more cellulose esters or ethers in admixture with a material or materials of another kind, for example cellulosic filaments, but particularly animal fibres such as wool or natural silk. A material containing cellulose acetate and cotton may for example be dyed a solid black in accordance with the present invention.

What we claim and desire to secure by Letters Patent is:-

1. Process for the production of black shades on materials comprising an organic derivative of cellulose, comprising oxidizing aniline thereon in the presence of mineral acid in quantity at least chemically equivalent to the aniline and in the presence of formic acid.

2. Process for the production of black shades on materials comprising cellulose acetate, comprising oxidizing aniline thereon in the presence of mineral acid in quantity at least chemically equivalent to the aniline and in the presence of formic acid.

3. Process for the production of black shades on materials comprising an organic 'derivative of cellulose, comprising oxidizing aniline thereon in the presence of mineral acid in quantity chemically equivalent to the aniline and in the presence of formic acid.

4. Process for the production of black shades on materials comprising cellulose acetate, comprising oxidizing aniline thereon in the presence of mineral acid in quantity chemically equivalent to the aniline and in the presence of formic acid.

5. Process for the production of black pattern effects on materials comprising an organic derivative of cellulose, comprising the oxidation of aniline present locally on the materials in the presence of mineral acid in quantity at least chemically equivalent to the aniline and in the presence of formic acid.

6. Process for the production of black shades on materials comprising an organic derivative of cellulose, comprising printing the materials with compositions containing aniline and oxidizing the aniline in the presence of mineral acid in quantity chemically equivalent thereto and in the presence of formic acid.

'7. Process for the production of black shades on materials comprising cellulose acetate, comprising printing the materials with compositions containing aniline and oxidizing the aniline in the presence of mineral acid in quantity chemically equivalent thereto and in the presence of formic acid.

8. Process for the production of black shades on materials comprising an organic derivative of cellulose, comprising applying to the materials a composition containing aniline and an oxidizing agent, and effecting oxidation in the presence of mineral acid in quantity at least chemically equivalent to the aniline and in the presence of formic acid.

9. Process for the production of pattern effects on materials comprising cellulose acetate, comprising printing the materials with a composition containing aniline, mineral acid in quantity chemically equivalent to the aniline, formic acid, and a chlorate, and ageing to effect oxidation of the aniline.

GEORGE HOLLAND ELLIS. HENRY CHARLES OLPIN. WILLIAM BERTRAM MILLER. 

